Production of tetryl and ethyl tetryl



Jan, 6, 1925.

1,522,025 T. J. NOLAN ET AL Paonuc'rrou OFYTETRYL AND Lin-rm. 2mn.

Fied nec. 2,4, 192s CH'N-CHI,

*j 2 g i Si 2 rPatented l H v if omPANY, AcoRPonarrIoN oF DELaWaRnL J l.k I n IRQDUCTIOJN QF TETR'YI AND E THYLpT'ETRYL: 1 Application mednecember 24,1923 senat 11011682543.

To aZZ whomiz't mag/[concern: I Theffobjectyof thepresentinventionw Beitknown that: we'VTHoMAs 'Jos-EPH provide processes for the manufacture-of-NOLAN and HENRY'VVILLEIAMy CLAPHKM, both `tetryl "and, its i ethylhomolgue 4kfree44 from? vsubjects of the Ki'ngof4 Great 'Britain andsuch disadvantages of danger in manufac? I vIreland,`an'd both residingat Ardee'rffFacturef.I and lack.` ofy-'stability` inthe' finished Ytory, Stevenston, Ayrshire,l zScotland, have A\productfasarereferred toabove;v

#6o invented 'certain' new and useful Improve- .The invention consistsin thejnitrationin Y v ments in and Relating tothe Production of -;tl1epresenceof; sulphuric acid-of anfalkyl--kv l-Tetryl and Ethyl Tetryl, ofwhich l`the folfphenylfnitrosamine; particularly thecon- 10-10wing isa-specicat-ion. u l version l:oi'v yimonomethylanilin'e or monof This'invention-relates to the nitration ,of ethylaniline'-intothe-nitrosamine-.and more 65 alkylphenylnitrosamines and yparticularlyparticularly followed by the nitration lof n -`to the manufacture'oftetryllthat is, 214:6- `the...,latter lirrvthepresence ofrsulphuric acidtrinitro-phenylmethyl-nitramine and;z-its-.into tetryl; or ethylitetryl, 15' ethylfhomologue or ethyltetryl, namely,y .c In carryingthey invention into effect in 2:4: 6#trinitro-phenylfethyl-nitramine oneform by lway ofoexample in connection 70 The' diagram illustrates t thegraphical with the preparation of tetryl, methylaniv'formulae ot-severalbodies referred! to below. li-neisfconverted in the ordinary way into sIny the' manufacture of. tetryl, as or'di-r methylf-fphenyllnitrosamine(see diagram)` f narily carried out, Y`dimethylaniline, (seeby treatingasolution of-.methylanilinein (iiagrariri)l is treated with nitric acidin' thewhydrochloric lacid with the requisite propor- 7,5 presenc'eofvsulphuric'acid, whereby nitration of sodiumnitrate solution;` y Theycrude tioniofthe arom'aticring takes -place andfnitrosalmine whichseparates out llasl an'oil, one of the methyl groups attachedftonthav is'thoroughly nwashed, withfwater; -30iparts iaminic nitrogen yatom is'replaced `by, the?, ott-he'.n'itrosa'minesofobtainediare dissolved l ilgroup NO2 formingtetryl `(see` diagram);b inOO partsof sulphuric acid{98,perfcent) S0 f Inf this reaction-a considerable-.amount maintainedat0f Gwand the-resulting solu-z of nitric acid is *usedup in oxidizingthe tion thenslowlyaddedto83A parts of n itricrv. methyl group displacedfrom combination1;racid'(92gpercent),,-the,temperatureofnie` with 'the'aminic nitrogen'atom, .Attempts i. tration being;maintainedlbetween50,and ff have beenfmade to use as araw material 559 C.,`. agitation of.the mixture'being ef- Q85 for the manufacturesiof tetryl monomethylflvfectcdgby mechanical' stirring.,v Tetrylsepai Vaniline andfthus obviatethe loss :of nitric v`rates out. The tem'perature,ofthelreaction i A5otrinitro-phenyl-ethyl-nitramine, ,bythe-nii;monornethylaniline.l i

acid incurred from the above causes 'when massismaintainedat 55,C. forone/hour, 35. dimethylaniline is used, butit has .been -fbyzexternal-heating. The mass is` .then,al

to y, j

found that the product soy obtained. isof lowedtocool to"v 15Giandfthetetryl sepa- -90 r i most unsatisfactory quality. In largescale [rated fromr-thelwasteacid and vwashedtree i #operations a `largeamount ot resinous,ma`from ,acidgby repeated boiling with water. 1lterialiis formed -which impedes'theaction The 4nitratvonIVoti;pmethylphenyl-nitrosf 4K0v 'of the stirring gear of-thevesselsused in' lamine to tetrylvisfcharacterizedbyfthe Ease themanufacture and may .give rise to f-fire;,.withwhich itcanbecontrolled;,the reaction 4even'under the bestv conditions the resultingproceeds much more smoothly than ingthe ""tetryl is contaminated with -aconsiderable case ofthe*n-itrationofl dimethylanilinathe.y proportionofi abody m-nitro-tetryll (seel: heat liberatedv being apparently muchless 45 diagram); v Y v than inkthe latteriinstance.v i

This material has an adverse eie'ctonthe In the nitration asvcarriedoutin ythis way 100'" stability of the product. ff noappreciable-amountolmetarnitroftetiyl In the manufacture ot the/'ethylhomolis' produced-and, `theqprocess is free fofthe, v

"llogueynamely, ethyl tetryL; that `is2:"4:'6A mechanical -diiiicultiesreferredlfto ,in using tration of tehyl Vaniline we have found that i,In carr ing. out the invention,in? another 105 similarv difficultiesoccur, a substantial profwayinwhich'we utilize. the monomethylaniportionof resinousfrnaterial 'contaminating linef'in,I mixturesofmorromethylanilineand,y the product. dimethylaniline, the so-calledcommercialv lfollows:` Page 1, llne 51, for the word tehylread ezy/Z;page 2, line 7, forthe Word nitrate read nitrite; lemol that the saidLetters, Patent l record of the oase in the Patent Office.` Y "n 4lSigned and sealed this 10th day of February, A. D. "1925,

[SEAL] Certificate of Correction.`

Itis hereby certid that in' Letters Patent lNo. 1,522,025, grantedJennery 6,

1925, upon the application of Thomas .,oseph Nolan and Henry WilliamClapham, of Stevenston.

Ethyl 'Tetrylj7 errors appear in the printed specification requiring'correction as i .KARL FENNINQ AotmgUmm/sszoner of Patents.

Scotland, foran improvement in The'Production of Tetryl and Y

